Azodyestuffs insoluble in water and fiber dyed therewith



Patented July 14, 1936 a.

UNITED:

- V 2,047,515 r .AZODYESTUFFS msoLUfiLEIN WATER AND 4 FIBER: DYED THEBEWITH 7 ur. Zitscher, Offenbachy, assignors to General New Ydlk N. Y d (idipol'ieonold jaslra {Arth 'oii-the-Main, German Aniline Works; Inc, I ration-voi Delaware Noiiiawiiig.

Our present invention relates tdnew azodyestuffs insoluble in water and to fiber dyedtlierd These dyestuifs contain' as typical component twice the arylamide of the following formula:

wherein n means the number 1 M2 nd R a; benzene or naphthalene nucleus which may besubstituted by alkyl, alkoxy, halogenornltr'o groups. In the molecule of our new-dyestuifs-twicethe aforesaid arylamide is attached by means ofazo groups torone radical of th-e'group consisting'of diphenyl, azobenzene, phenyl azoen aphthalene, phenylamino-phenyl-azobenzene which radicals may contain alkyl, alkoxy,nhalogen,. nitro groups or an acylamino-group. p I c V In consequence of the fact that the L-m'ethyI- {l-hydroxy-benzene-radical of the above formula may be once or twice attached to the radical R by means of CO-NH-groups" (which groups are named throughout this specification f"carb'onylamino) and that it is twice" attached by'means of azo groups to the radical of the aforesaid group, a general formula covering all'thedye- Stuffs forming h s s Oi plulmosent in ntion e t a erenared,,.hr..comb n nc th tetrazo compound of the; group-consisting; of, d

phenylamino-phenyl-az obenzene' whioh' mayl con;-

8 tain alkyl, alkoxy, halogen nitro groups or an m eo-group a ws l s lt en s. wi h r-lia amide of the aboveformula V The dyestunfs may be advantageously produced on acetate silk according to the developing methd Zi' 5.

In this-manner yellow to -browndye'ih sateen: tained which could-hither-t not 6* rodilcd iii alike: beauty and multiplicity off-'shtides- 'I 'liese dyeingsare distinguished ai =-good *-fasfiie's's especiallytocross dyeingi v Inord'erto further illustrate -ourinyention'; t e

following exampl'es-are g1-venz- We'w1sii1t, new

ever, to be understood that we are not limited to the particular products or reaction conditions mentioned therein. 7 Example 1 Acetate silk is" impregnated at 6'0 C. in a solution, containing per liter' 1 gr. of 4,4'-diamlno-3,3'-dimethoxy-diphenyl, 2 cc. of hydrochloric acid of 2 ,nd' .-.l -r.se.or sodium; acetate-1 Then the goods are tetrazctizedfinitheriisualaman er and developed in a solutioni containing. per liter 2 grs. of 1-(4-hydroxy{1 methyiabenzenefiie carbonyl) amino-2-methylbenzeneA cccof cans 05 t c da-s lu on 911,345.Biiahdezpci or Turkey ()FFICE ppll'cation August 27, 1931; Serial No. 55%);812. fr'fGermanySeptember 1 1930 501M} -(Cl. 260 -72) After rinsing and soaping a yellowish eing of a very good fastness to crossdyeiri'gis-o'btained.

The dyestuif thus produced on the fiber corresponds to the formula:

1- methyl-benzene-3- caryl-benzene is v r W -;(4- d oxybonyl) arnino-Z-meth (4-. hydroxy-l-methyl-benzeneno-benzene, a, dark reddish b similar fastness is obtained.

3p-carbonyl) -amiro-wn dyeing of a cetate; 'Ih'e'n e'vel'ope'd in a r 2 g'rslof 1*-(4'-hy- 3- -carbonyl)-amino 2- e, 4 cc. of caustic soda Be. and 2 cc. of Turkey redoil. in the usual way a yelowish yeing of a very good fastness is dyestufi thus produced on the fiber compound yields with (4'-'hy nzene 3 7- carbonyl)" +aininobrown dyeing.

v Examples!v 1 mpregnat-ed in a'bathcontain- L- of 4,4diamin0 2;2'-dichlbro= drochloric acid of -20 B; and The goods" are tetra a bathcontaining" per -'hy'd'rox3'f--1'-inetliyl beif 2-,5-dimethoxy -berizen ion of 34P'B: and? c ta te-east. droxy- I-methyl-be benzene, a neutral of 'Iurkey red oil. After finishing in the usual mannera full yellow dyeing of a very good fastness is obtained.

4,4-diamino-2-methy1-5-methoxyazobenzene yields with the same combining component an orange brown dyeing.

With other diamino compounds of the above mentioned kind and with other arylamides of 4- hydroxy-1-methyl-benzene-3-carboxylic acid the process may be likewise carried out.

The following table shows for example the shades of some dyestuffs of this kind:

(4-hydroxy-1-methy1benzene-3- carbonyl) aminobenzene yields with the tetrazo-compound Shade 4-amino-l-(4' amino-phenyl-azo) naphthalene Reddish brown 4-amino-1-(4'-amino-2'-methyl-5' methoxyphenyl-azo)-naphthalene Brown 4,4'-diamino-5 methoxy 2 chloro-azo-benzene Yellowish brown 4,4-diamino-2-nitro-diphenyl 01d gold 1 (4-hydroxy-1-methyl-benzene-3 carbonyl) amino-Z-methyl-benzene yields with the tetrazo-compound of:

Shade 4,4 -diamino-2,5,2'-trimethoxy-azobenzene Full reddish brown 4,4-diamino-3,3-dimethoxy-diphenyl Yellowish brown 4,i' hllififfi ifi ifiiififiiieuyi- Yellow 4 amino 4 (4"-amino-pheny1-amino) 2 methyl-5-methoxy-azo-benzene Neutral brown 4,4 diamino-Z methyl-5-methoxy 2'- chloroazo-benzene Yellowish brown 4-amino-3-ethoxy-1- (4' amino-phenyl-azo)- naphthalene Yellowish brown 4,4-diamino-2- acetyl-amino 5 methyl 2' chloro-azo -benzene Reddish brown 1 (4-hydroxy-l-methyl-benzene-3-carbonyl) amino-Z-methoxy-benzene yields with the tetrazocompound of:

' Shade I 4,4-diamino- 2,5-' dirnethyl 2' methoxy-azobenzene Yellowish orange-brown 4,4-diamino-3,3-dimethoxy-dipheny1 Yellowish brown- 4,4'-diamino-2-methyl- 5,2 dimethoxy azobenze Brown l.(4 hydroxy-l-mcthyl-benzene-S -carbonyl) ,amino-2-methyl-4-methoxy-benzene yields with the tetrazocompound of:

Shade 4,4 -diamino-2,5-dimethyl-2'-chloro-azo bed-'- zene Yellowish orange-brown 4,4-diamino-3,3dimethoxy-diphenyl Yellowish brown benzene Yellowish brown 4,4'- diamino-2-methyl 5,2 dimethoxy azobenzene Reddish brown 4,4'-diarnino-2,5-dimethoxy 2' chloro azo- V benzene Reddish brown 1- (4-hydroxy-1-methyl-benzene-3 carbonyl) amino-S-nitro-benzene yields with the tetrazocompound of:

Shade 4,4-diamino-3,3-dimethoxy-diphenyl Olive brown 4,4'-dlamino-2-methyl-5- methoxy azo benzene Full brown 1- (4-hydroxy-l-methyl-benzene-B carbonyl) amino-naphthalene yields with the tetrazocompound of:

Shade 4,4-diamino-3,3'-dimethoxy-diphenyl Neutral brown 4,4-diamino-3,3'-dichloro-diphenyl Yellowish orange-brown 2- (4-hydr0xy-1-methyl-benzene-3 carbonyl) amino-naphthalene yields with the tetrazocompound of:

Shade 4,4-diamino-2-methyl-5 methoxy azo benzene Dark brown 4,4-diamino 2,5-dimethyl-2-chloro-azo benzene Brown 4,4-diamino-2,5,2'-trimethoxy-azo benzene Blackish brown 4,4'-di-(4-hydroxy-l-methyl-benzene 3 carbonyl amino) 3,3 dimethoxy diphenyl yields with the tetrazocompound of:

Shade 4,4-diamino-3,3'-dimethoxy-diphenyl Yellowish orange-brown 4,4-diamino-2,5,2-trimethoxy-azo benzene Full reddish brown 1,4-di (4-hydroxy-l-methyl-benzene- 3 -carbonyl-amino) -2 methyl 5 methoxy benzene yields with the tetrazocompound of:

Shade 4,4-diamino-3,3-dimethoxy-diphenyl Yellowish brown 4,4-diamino-2-methyl- 5,2 dimethoxy azobenzene Brown 4,4-diamino-2-methyl-5-methoxy- 2 chloroazo-benzene Orange brown 4,4-diamino-2',5 '-dimethyl 3 methoxy-azobenzene Orange brown 4,4'-diamino-2,2-dich1oro-diphenyl Yellow 4-amino-4- (4"- amino phenyl amino) 2 methyl-5-methoxy-azo-benzene Brown we claim:

1. As new compounds the azodyestufis obtained by combining a tetrazo-compound of a radical of the group consisting of diphenyl, azobenzene, phenyl-azo-naphthalene, phenylamino-phenylazobenzene which radicals may contain alkyl, alkoxy, halogen, nitro-groups or an acylaminogroup with an arylamide of the formula:

mc 5 00-NH- '11 wherein 11. means the number 1 or 2 and R a benzene or naphthalene nucleus which may be substituted by alkyl, alkoxy, halogen or nitro-groups, which compounds are insoluble in water and yield when produced on acetate silk yellow to brown dyeings of a-good fastness to cross-dyeing.

general formula:

wherein the benzene nuclei not containing the hydroxy groups may contain alkyl, alkoxy, halogen or nitro-groups and X means a C-C-bond or an azo-group, which compounds are insoluble in Water and yield when produced on acetate silk yellow to brown dyeings of a good fastness to cross-dyeing.

3. As a new compound the azodyestufi of the formula:

(I) C Ha we which compound is insoluble in water and yields when produced on acetate silk yellowish brown dyeings of a good fastness to cross-dyeing.

4. As a new compound the azodyestufi of the formula:-

U HI G T 5 AH; OH

com -OH 15 which compound is insoluble in water and yields 20 when produced on acetate silk neutral brown dyeings of a good fastness to cross-dyeing.

5. The azodyestufis obtained by combining a, ;diazotized aromatic amino compound and an arylide made by condensing a hydroxy-carboxylic 25 acid of the benzene series which is substituted by a methyl group in the para-position to the OH group, with primary aromatic amines of the benzene, naphthalene and diphenyl series.

6. Fiber dyed with the azodyestufis as claimed in claim 1.

7. Fiber dyed with the azodyestufis as claimed in claim 2.

8. Fiber dyed with the azodyestuif as claimed in claim 3. 9. Fiber dyed with the azodyestuff as claimed in claim 4.

LEOPOLD LASKA. ARTHUR ZITSCHER. 

